US4702858A - Washing agents containing, as additives, carboxyl-containing copolymers which are neutralized or amidated with amines - Google Patents

Washing agents containing, as additives, carboxyl-containing copolymers which are neutralized or amidated with amines Download PDF

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US4702858A
US4702858A US06/888,957 US88895786A US4702858A US 4702858 A US4702858 A US 4702858A US 88895786 A US88895786 A US 88895786A US 4702858 A US4702858 A US 4702858A
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Walter Denzinger
Heinrich Hartmann
Wolfgang Trieselt
Erhard Klahr
Albert Hettche
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

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  • the carboxyl-containing homo- and copolymers described above are in each case partially or completely neutralized with amines of the formula I.
  • the copolymers are in the form of aqueous solutions, an amine of the formula I is added either directly or as a solution in water.
  • the carboxyl-containing polymers are in the form of a powder, they are introduced into water, and the amines of the formula I are then added.

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  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Washing agents contain, as additives for inhibiting redeposition and promoting the primary washing action, homopolymers of acrylic acid and of methacrylic acid, copolymers of acrylic acid and methacrylic acid and copolymers which contain, as essential components,
(a) an ethylenically unsaturated dicarboxylic acid of 4 to 6 carbon atoms and
(b) acrylic acid, methacrylic acid and/or hydroxy-C2 -C6 -alkyl esters of ethylenically unsaturated C3 -C6 -carboxylic acids as copolymerized units,
where the homo- and copolymers in the form of the free acids have a weight average molecular weight of from 5000 to 500,000 in the neutralized or amidated form, the carboxyl groups of the homo- and copolymers in each case being partially or completely neutralized with amines of the formula ##STR1## where R is C8 -C18 -alkyl or R1 --O--CH2 --(CH2)n --, n is from 1 to 3, R1 is C1 -C18 -alkyl, R2 and R3 are each H or C1 -C18 -alkyl and/or from 5 to 50% of the said carboxyl groups being in the form of amides derived from primary and secondary amines of the formula I.

Description

U.S. Pat. No. 3,706,672 discloses essentially phosphate-free washing agents which contain, as principle components, a detergent and an alkali metal or ammonium polyacrylate, which is present as a builder, in an amount of about 10-40%, based on the total mixture. The ammonium salts of the homopolymers are derived from, for example, methylamine and triethylamine. Although builders of this type impart a high sequestering power to the washing agents, they have no antiredeposition effect.
European Pat. No. 25,551 discloses the use of copolymers which contain, as copolymerized units, from 40 to 90% by weight of acrylic acid or methacrylic acid and from 60 to 10% by weight of maleic acid, as phosphate substitutes in washing agents. The copolymers are preferably employed in the form of sodium or ammonium salts. Although these copolymers contribute to the primary washing action of a washing agent and are very effective incrustation inhibitors, they make no contribution to the inhibition of redeposition.
It is an object of the present invention to provide an additive for washing agents and cleaning agents which is capable of completely or partly replacing the polyphosphates in washing agents or reinforcing the primary washing action of conventional washing agents, and furthermore has an adequate incrustation-inhibiting and antiredeposition action.
We have found that this object is achieved, according to the invention, by using homopolymers of acrylic acid and of methacrylic acid, copolymers of acrylic acid and methacrylic acid and copolymers which contain, as essential components,
(a) from 10 to 70% by weight of an ethylenically unsaturated dicarboxylic acid of 4 to 6 carbon atoms and
(b) from 90 to 30% by weight of acrylic acid, methacrylic acid and/or a hydroxy-C2 -C6 -alkyl ester of an ethylenically unsaturated C3 -C5 -carboxylic acid as copolymerized units,
where the homo- and copolymers in the form of the free acids have a weight average molecular weight of from 5000 to 500,000, in the neutralized or amidated form, the carboxyl groups of the homo- and copolymers being partially or completely neutralized with amines of the formula ##STR2## where R is C8 -C18 -alkyl or R1 --O--CH2 --(CH2)n --, n is from 1 to 3, R1 is C1 -C18 -alkyl, R2 and R3 are each H or C1 -C18 -alkyl and/or from 5 to 50% of the said carboxyl groups being in the form of amides derived from primary and secondary amines of the formula I, as an additive to washing agents and cleaning agents, in an amount of from 0.5 to 10% by weight, based on the solids, the said additives inhibiting redeposition and promoting the primary washing action.
Homopolymers of acrylic acid and of methacrylic acid are known. They are prepared, for example, by polymerization of acrylic acid or methacrylic acid in aqueous solution in the presence of polymerization initiators and, if required, polymerization regulators at from 50° to 150° C. At above 100° C., the polymerization has to be carried out in pressure apparatuses. The molecular weights of the polyacrylic acids and polymethacrylic acids used according to the invention are from 5000 to 500,000, preferably from 10,000 to 300,000. Copolymers of acrylic acid and methacrylic acid which may contain the two monomers in any ratio can also be used according to the invention. The molecular weight range of the copolymers of acrylic acid and methacrylic acid corresponds to that of the homopolymers.
Particularly suitable copolymers for achieving the above object are those which contain, as essential components and as copolymerized units,
(a) from 10 to 70% by weight of an ethylenically unsaturated dicarboxylic acid of 4 to 6 carbon atoms and
(b) from 90 to 30% by weight of acrylic acid, methacrylic acid and/or a hydroxy-C2 -C6 -alkyl ester of an ethylenically unsaturated C3 -C5 -carboxylic acid,
the sum of the percentages always being 100, and which have a weight average molecular weight of from 5000 to 500,000, preferably from 10,000 to 200,000. The copolymers are prepared by copolymerization of one or more monomers from group (a) with one or more monomers from group (b) by a conventional method (cf. Australian Application No. 70 571/81). The ethylenically unsaturated dicarboxylic acids of 4 to 6 carbon atoms are, for example, maleic acid, fumaric acid, aconitic acid, itaconic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The copolymers used according to the invention preferably contain maleic acid and/or itaconic acid as copolymerized units. The said dicarboxylic acids may furthermore be subjected to copolymerization in the anhydride form. For example, it is particularly easy to subject maleic anhydride to copolymerization with the monomers of group (b) and, if desired, other monomers. The copolymers containing maleic anhydride units and formed in the absence of water hydrolyze very rapidly in an aqueous medium to give the corresponding copolymers which contain maleic acid units; the latter copolymers can then be reacted with amines to give the salts of the copolymers containing maleic acid units or, when the reaction is carried out in the absence of water, to give the amides.
The copolymers contain, as component (b), one or more monomers from the group consisting of acrylic acid, methacrylic acid and hydroxy-C2 -C6 -alkyl esters of ethylenically unsaturated C3 -C5 -carboxylic acids, as copolymerized units. Suitable hydroxyalkyl esters are obtained by reacting ethylenically unsaturated C3 -C5 -carboxylic acids with C2 -C6 -alkanediols. Suitable alkanediols are glycol, propane-1,3-diol, propane-1,2-diol and mixtures of the propanediols, butane-1,4-diol, butane-1,3-diol, butane-2,3-diol and mixtures of the isomeric butanediols, pentane-1,5-diol and hexane-1,6-diol. Examples of suitable hydroxyalkyl esters are hydroxyethyl acrylate, 2-hydroxypropylacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and hydroxyhexyl acrylates. The use of acrylic acid, as a monomer of group (b), and of mixtures of acrylic acid or methacrylic acid and hydroxyethyl acrylate or hydroxypropyl acrylates is particularly preferred. These monomers can be copolymerized in any ratio with the monomers of components (a). Where two or more monomers of group (b) are used in the copolymerization, these mixtures advantageously contain from 5 to 70% by weight of acrylic acid and from 95 to 30% by weight of a hydroxyalkyl ester of an ethylenically unsaturated C3 -C5 -carboxylic acid as copolymerized units. In addition to the hydroxyalkyl esters of acrylic acid and methacrylic acid, other suitable monomers of group (b) are the hydroxyalkyl half esters and esters of maleic acid, fumaric acid and itaconic acid. The copolymers contain from 90 to 30, preferably from 80 to 40, % by weight of the monomers of group (b).
The copolymers can, if required, be modified by copolymerizing, during the polymerization, up to 15% by weight, based on the monomers (a) and (b), of monomers of group (c), which include, for example, acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, vinylphosphonic acid, allylphosphonic acid, vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate and styrene. From this group of monomers, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, vinyl acetate and vinyl propionate are preferably used.
The weight average molecular weight of the copolymers of the monomers (a) and (b) and, where relevant, (c) is from 5000 to 500,000, preferably from 10,000 to 200,000.
The homo- and copolymers described above are partially or completely neutralized with amines of the formula I ##STR3## where R is C8 -C18 -alkyl or R1 --O--CH2 --(CH2)n --, n is from 1 to 3, preferably 1, R1 is C1 -C18 -alkyl, R2 and R3 are each H of C1 -C18 -alkyl, or are partially converted to the amides by reaction with the primary and secondary amines of the general formula (I). Examples of suitable amines of the formula I are octylamine, nonylamine, decylamine, 6-methyl-2-heptylamine, 2-ethylhexylamine, tridecylamine, mono-(C12 /C14)-amines, palmitylamine, stearylamine, tridecyloxypropylamine, isopentyloxypropylamine, n-butoxypropylamine, stearyloxyethylamine, N-methyl-N-tridecylamine, dimethyltridecylamine, stearyloxypropylamine, di-2-ethylhexylamine, N,N-dimethyl-2-ethylhexylamine, di-2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-(2-ethylhexyloxy)-propylamine, di-n-octylamine, diisononylamine, diisotridecylamine, tri-n-octylamine, triisooctylamine, triisodecylamine and 3-isononyloxypropylamine.
Preferably used amines of the formula I are those in which R is C10 -C16 -alkyl and R2 and R3 are each hydrogen or C1 -C4 -alkyl.
The carboxyl-containing homo- and copolymers described above are in each case partially or completely neutralized with amines of the formula I. Where the copolymers are in the form of aqueous solutions, an amine of the formula I is added either directly or as a solution in water. Where the carboxyl-containing polymers are in the form of a powder, they are introduced into water, and the amines of the formula I are then added. However, it is also possible to introduce a pulverulent carboxyl-containing polymer and an amine of the formula I simultaneously into water, neutralization then taking place. Conversely, it is also possible to add an aqueous solution or an aqueous dispersion of a carboxyl-containing polymer to an amine of the formula I or to an aqueous solution of the amine of the formula I. The amount of amine of the formula I is chosen so that the carboxyl groups of the polymers are completely or partially neutralized with the said amine. The degree of neutralization of the carboxyl groups of the polymers is from 1 to 100%, preferably from 20 to 100%. When the carboxyl-containing polymers are neutralized with the amines of the formula I, clear solutions, cloudy solutions or aqueous dispersions are obtained. The different solubilities of the neutralized or partially neutralized carboxyl-containing polymers has virtually no effect on the activity of these products in washing agents. If the polymers are only partially neutralized with the amines of the formula I, it is also possible to use sodium hydroxide solution, potassium hydroxide solution, ammonia, C1 -C4 -alkylamines, ethanolamine or triethanolamine until the copolymers are completely neutralized, if this is desirable for improving the solubility of the products. The solutions or dispersions of the homo- or copolymers partially or completely neutralized with the amines of the formula I can be incorporated directly into the washing agents or the said homo- or copolymers may be isolated from the aqueous solution by evaporating the water and added in the form of a powder to the washing agent formulation.
The amides of the homo- and copolymers described above are obtained by reacting these polymers, in the absence of water, with primary or secondary amines of the formula I, the amount of these amines being chosen so that from 5 to 50, preferably from 10 to 35, % of the carboxyl groups of the homo- and copolymers are converted to the corresponding amide. The amidation may be carried out, for example, in an inert solvent, such as xylene, toluene, tetrahydrofuran, dioxane or methyl tert-butyl ether, at from 20° to 140° C., preferably from 40° to 80° C. However, the only amines of the formula I which are suitable for the amidation are primary and secondary amines. For the amidation, R2 in the general formula I is preferably C1 -C4 -alkyl, while R3 is hydrogen. The amidation is preferably carried out using primary amines in which R is C10 -C16 -alkyl and R2 and R3 are each H, or secondary amines of the formula I in which R is C10 -C16 -alkyl and R2 is C1 -C4 -alkyl.
The amide-containing copolymers are preferably prepared from copolymers of maleic anhydride as component (a) and the compounds (b), because maleic anhydride forms the amide in a smooth reaction with the primary or secondary amines of the formula I.
Amidation of carboxyl-containing homo- and copolymers of the type described above with the amines of the formula I gives amides or mixtures of the corresponding amides and the neutralized carboxyl-containing polymers, depending on the procedure used. Of course, the tertiary amines of the formula I give only the salts of the hydrolyzed carboxyl-containing polymers.
However, amides used according to the invention can also be obtained by subjecting amides of ethylenically unsaturated dicarboxylic acids of 4 to 6 carbon atoms and primary or secondary amines of the formula I to copolymerization with the monomers (b) and, if required, (c). The amides of copolymers of components (a) and (b), which are used according to the invention, are preferably prepared using monomaleamides which are derived from amines of the formula II ##STR4## where R is C8 -C18 -alkyl or R1 --O--CH2 --(CH2)n --, n is from 1 to 3, R1 is C1 -C18 -alkyl, R2 is H or C1 -C18 -alkyl and R3 is H.
Examples of suitable monomaleamides are N-(isopentyloxypropyl)-monomaleamide, N-(tridecyloxypropyl)-monomaleamide, N-(n-butoxypropyl)-monomaleamide and N-(isopropoxypropyl)-monomaleamide.
The above homo- and copolymers which have been converted to the neutralized or amidated form by reaction with the amines of the formula I are added to washing agents and cleaning agents in an amount of from 0.5 to 10, preferably from 1 to 5, % by weight, based on the solids, in order to inhibit redeposition and to promote the primary washing action. The salts or amides used according to the invention can be incorporated in the form of an aqueous solution, an aqueous dispersion or a powder into washing agents and cleaning agents. They reinforce the primary washing action and secondary washing action of conventional washing agent and cleaning agents and can furthermore be used for partly or completely replacing polyphosphates in washing agents. The homo- and copolymers used according to the invention and neutralized or amidated with amines of the formula I are particularly useful for the production of washing agents based on surfactants, builders (polyphosphates, zeolites, nitrilotriacetic acid, sodium carbonate and silicates) and bleaches (perborates) and, if required, conventional additives (eg. antifoams, perfume, optical brighteners and enzymes) and fillers, such as sodium sulfate. Washing agents of this type are either phosphate-free or contain not more than 25% by weight, calculated as sodium tri-polyphosphate and based on the total washing agent formulation, of polyphosphate. The carboxyl-containing polymers used according to the invention and neutralized or amidated with the amines of the formula I are present in the washing agents, in an amount of from 0.5 to 10, preferably from 1 to 5, % by weight, and, apart from reinforcing the primary washing action, inhibit incrustation and redeposition in the textile material. These washing agents have a particular white wash action and furthermore protect the washed white material from redeposition. The substances used according to the invention thus have the effect of improving the removal of dirt from the soiled textile materials, but substantially preventing redeposition of the dirt onto the textile material, even when the wash liquor has a fairly high dirt load. Of particular industrial importance is the fact that the antiredeposition action is effective not only in the case of pure cotton but also to a substantial extent in the case of the widely used cotton/polyester blends.
In the Examples, parts and percentages are by weight. The K values were measured according to H. Fikentscher, Cellulose-Chemie 13 (1932), 58-64 and 71-74, in a 1% strength aqueous solution at 25° C. and pH 7, unless a different solvent is mentioned. In all cases, K=k. 103.
The weight average molecular weights of the carboxyl-containing polymers were determined by gel permeation chromatography (GPC) using aqueous eluents. The separation columns were calibrated with polystyrenesulfonates which had a narrow molecular weight distribution and were obtained from Pressure Chem. Corp. The values thus obtained were converted to the molecular weights of polysodium acrylate by the universal calibration principle due to BENOIT (J. Chim. Phys. 63 (1966), 1507), using the measured data of SPATORICO and BEYER (J. Appl. Polym. Sci. 19 (1975), 2933).
Preparation of additives 1 to 8 used according to the invention.
In a 4 L glass reactor provided with a reflux condenser, a stirrer and a nitrogen inlet line, 750 parts of xylene, 4.29 parts of polyethyl vinyl ether having a K value of 50 (determined in cyclohexanone at 25° C.) as a 70% strength solution in toluene, and 375 parts of maleic anhydride are heated at from 80° to 85° C. in a gentle stream of nitrogen. A solution of 300 parts of maleic anhydride in 300 parts of xylene is added in the course of 2 hours and at the same time, but in the course of 3 hours, 825 parts of acrylic acid are introduced, and a solution of 12 parts of tert-butyl perethylhexanoate in 300 parts of xylene is metered in over a total period of 4 hours. When the addition of the initiators is complete, the contents of the reactor are heated to the boil (133° C.). As soon as the boiling point is reached, a solution of 12 parts of di-tert-butyl peroxide in 150 parts of xylene is added in the course of 1 hour, and the reaction mixture is heated at the boil for a further hour and then left to cool. A copolymer of maleic anhydride and acrylic acid is obtained in the form of a slightly viscous, fine-particled suspension. The K value of the copolymer is 42. The suspension has a solids content of 49.9% and is reacted with the amines stated in Table 1 in order to prepare the additives 1 to 9. The copolymer has a weight average molecular weight of 45,000.
To prepare additives 1 to 9, 200 parts of the suspension described above are initially taken in each case in a 500 ml flask which is provided with a stirrer and a nitrogen inlet and outlet. The suspension is stirred, and heated to 70° C. As soon as this temperature is reached, the particular amine stated in Table 1 is added. Thereafter, the reaction mixture is stirred at 70° C. for a further 2 hours, after which the amount of water likewise stated in Table 1 is added. The suspending agents (xylene and toluene) are then removed at 110° C. by passing in steam, and the mixture is cooled to give an aqueous dispersion of the additives 1 to 9, whose solids contents are likewise given in Table 1.
              TABLE 1                                                     
______________________________________                                    
                                     Solids                               
Additive                                                                  
       Amine added,        Amount of content                              
No.    parts               H.sub.2 O added                                
                                     (%)                                  
______________________________________                                    
1      51      tridecylamine   128     32.6                               
2      27.8    tridecylamine   128     24.8                               
3      74.2    tridecylamine   128     31.4                               
4      29.6    2-ethylhexylamine                                          
                                96     42.6                               
5      61.9    stearylamine    146     33.3                               
6      73.1    mono-(C.sub.12 /C.sub.14)--amine                           
                                96     60.6                               
7      120.3   stearyloxypropylamine                                      
                                96     23.2                               
8      94.4    tridecyloxypropylamine                                     
                               246     32.4                               
______________________________________
Additives 9 to 11
750 parts of xylene, 4.29 parts of the polyethyl vinyl ether stated above and 250 parts of maleic anhydride are initially taken in the polymerization reactor described above, and are heated to 85° C. in a gentle stream of nitrogen. 200 parts of maleic anhydride are then added in the course of 2 hours at this temperature and at the same time, but over a period of 3 hours, 1050 parts of acrylic acid are introduced, and a solution of 12 parts of tert-butyl perethyhexanoate in 300 parts of xylene is added continuously in the course of 4 hours. The reactor contents are then heated at the boil and a solution of 12 parts of di-tert-butyl peroxide in 150 parts of xylene is added in the course of 1 hour, after which the mixture is heated at the boil for a further hour and then cooled. A fine-particled suspension of a copolymer of maleic anhydride and acrylic acid, having a K value of 52, is obtained. The weight average molecular weight is 75,000, and the suspension has a solids content of 49.9%.
The additives 9 to 11 are obtained by heating, in each case, 200 parts of the suspension described above in a 500 ml flask, in a nitrogen atmosphere at 70° C., while stirring, and adding the amines stated in Table 2 in the amount likewise stated there, in the course of 1 hour. When the addition of the amine is complete, the reaction mixture is heated for a further 2 hours at 70° C., and the amount of water stated in Table 2 is added and the mixture is freed from the suspending agent by passing in steam. A dispersion is obtained in each case, its solids content being shown in Table 2. Additives 10 and 11 are additionally neutralized with 50% strength aqueous sodium hydroxide solution (cf. Table 2).
              TABLE 2                                                     
______________________________________                                    
                       Amount   50%                                       
                       of H.sub.2 O                                       
                                strength                                  
                                       Solids                             
Additive                                                                  
       Amine added,    added,   NaOH,  content                            
No.    parts           parts    parts  (%)                                
______________________________________                                    
 9     85.2   stearylamine 146    --     28.4                             
10     60.9   mono-(C.sub.12 /C.sub.14)--                                 
                           96     83     33.5                             
              amine                                                       
11     39.6   6-methyl-2-  96     88     30.0                             
              heptylamine                                                 
______________________________________
Additive 12
60 parts of water, 12 parts of maleic anhydride, 10 parts of sodium hydroxide and 116 parts of N-(isopentyloxypropyl)-monomaleamide are initially taken in a glass flask provided with a stirrer, a reflux condenser and a nitrogen inlet line and are heated to the boil, after which a solution of 72 parts of acrylic acid and 72 parts of water is added in the course of 5 hours. Together with the addition of the acrylic acid, a solution of 6.7 parts of 30% strength hydrogen peroxide and 2 parts of sodium persulfate in 70 parts of water is metered into the reaction mixture over a total period of 6 hours, and the reaction mixture is heated at the boil for a further hour after the initiators have been added. Thereafter, the reaction mixture is neutralized with 50% strength aqueous sodium hydroxide solution and is left to cool. A clear, reddish brown viscous solution having a solids content of 44.3% is obtained. The K value of the copolymer is 17.4, and the weight average molecular weight is 10,000.
Additive 13
60 parts of water, 10 parts of maleic anhydride, 9 parts of sodium hydroxide and 134 parts of N-(tridecyloxypropyl)-monomaleamide are initially taken in a polymerization vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet line and are heated to the boil. As soon as the mixture begins to boil, a solution of 56 parts of acrylic acid in 72 parts of water is added in the course of 5 hours and, separately from this, a solution of 6.7 parts of 30% strength hydrogen peroxide and 2 parts of sodium persulfate in 70 parts of water is introduced in the course of 6 hours. The reaction mixture is then heated at the boil for a further hour, after which it is neutralized with 70 parts of 50% strength aqueous sodium hydroxide solution and diluted with 150 parts of water. The resulting yellow, slightly cloudy solution has a solids content of 31.8%. The copolymer has a K value of 44.8 and a weight average molecular weight of 50,000.
Additive 14
60 parts of water, 20 parts of maleic anhydride, 14.7 parts of sodium hydroxide and 100 parts of N-(n-butoxypropyl)-monomaleamide are initially taken in a flask provided with a reflux condenser, a stirrer, a nitrogen inlet and metering apparatuses and are heated to the boil, a solution of 123.7 parts of acrylic acid in 72 parts of water is added in the course of 5 hours, and, separately from this, a solution of 7.6 parts of 30% strength hydrogen peroxide and 2 parts of sodium persulfate in 70 parts of water is added in the course of 6 hours. When the addition of the initiators is complete, the reaction mixture is heated at the boil for a further hour, after which it is neutralized by adding 100 parts of 50% strength aqueous sodium hydroxide solution. The resulting reddish brown, cloudy solution has a solids content of 44.4%. The copolymer of maleic acid and acrylic acid has a K value of 20.2 and a weight average molecular weight of 11,000.
USE EXAMPLES
The washing agent formulations I to VI shown in Table 3 are prepared, these formulations being low-phosphate or, in the case of formulation III, phosphate-free formulations. The effects obtained with these washing agent formulations are shown in the Tables below, in comparison with formulations according to the invention. If, however, the known formulations are additionally combined with from 2 to 3% by weight of the additives used according to the invention, eg. additives 1 to 14, and washing tests are then carried out with the washing agent formulations I to VI modified in this manner, an increase of up to 7 points for the whiteness on WFK soiled fabric is measured in the case of the primary washing action, thus demonstrating the substantial increase in this action. The good secondary washing action of the modified washing agent formulations I to VI is demonstrated by the same tests, in which unsoiled cotton, cotton/polyester fabric and polyester fabric are much less soiled after 5 washes together with WFK and EMPA fabric when the novel additives are present in the washing agent formulations I to VI.
The washing agent formulations I to VI are shown in Table 3.
              TABLE 3                                                     
______________________________________                                    
               Formulation example                                        
Washing agent component                                                   
                 I       II     III IV  V    VI                           
______________________________________                                    
Alkylbenzenesulfonate                                                     
                 5       6      6   6   5    6                            
Fatty alcohol oxyethylate +                                               
                 3       2      3   5   3    4                            
11 EO                                                                     
Soap based on coconut oil                                                 
                 3       3      3   3   3    3                            
Pentasodium triphosphate                                                  
                 20      20     --  20  10   10                           
Trisodium nitrilotri-                                                     
                 5       --     5   --  3    10                           
acetate                                                                   
Polyacrylic acid 3       --     --  --  2    --                           
Acrylic acid/maleic acid                                                  
                 --      3      4   1.6 1    5                            
copolymer                                                                 
Zeolite A        --      10     20  --  5    --                           
Sodium carbonate --      --     10  --  --   --                           
Phosphonates of the hydroxy-                                              
                 --      --     0.5 --  0.5  1                            
ethanediphosphonic acid                                                   
type                                                                      
Na silicate      6       5      6   10  6    7                            
Mg silicate      1       1      1   1   1    1                            
Na perborate     20      15     20  20  15   15                           
Pentaacetyl glucose                                                       
                 3       --     4   --  2    3                            
Tetraacetylethylene-                                                      
                 --      4      --  --  --   --                           
diamine                                                                   
Carboxymethylcellulose                                                    
                 0.8/0.2 --     --  --  --   --                           
hydroxypropylmethyl-                                                      
cellulose                                                                 
Vinyl acetate/vinyl pyr-                                                  
                 --      0.5    0.5 --  --   --                           
rolidone copolymer accord-                                                
ing to German Laid-Open                                                   
Application DOS 3,206,883                                                 
Ethylenediaminetetraacetic                                                
                 --      --     --  0.2 --   --                           
acid                                                                      
Standardizing agent:                                                      
                 27      27     14  30  40   32                           
sodium sulfate                                                            
Remainder to 100%: water                                                  
______________________________________
To test the mode of action of the washing agents, the following test conditions are maintained:
______________________________________                                    
Test apparatus:   Launder-o-meter                                         
Water hardness:   3.5 mmol/l (Ca:Mg = 80:20)                              
Amount of liquor: 250 ml                                                  
Liquor ratio:     1:10                                                    
Test temperature: 35-60° C.                                        
Test duration:    30 minutes (including heating                           
                  up time)                                                
Washing agent concentration:                                              
                  8 g/l                                                   
Number of washes: 5                                                       
Test fabric:                                                              
5 g of polyester (PES)   (1)                                              
5 g of polyester/cotton blend (PES/C)                                     
                         (2)                                              
10 g of terry cloth      (3)                                              
+ 2.5 g of WFK cotton standard soiled fabric.sup.( *.sup.)                
+ 2.5 g of pigment-soiled fabric.sup.( **.sup.)                           
______________________________________                                    
 .sup.(*.sup.) No. 10 C, obtainable from WFKTestgewebe GmbH, Adlerstr. 44,
 D 4150 Krefeld                                                           
 .sup.(**.sup.) Own manufacture. The fabric contains the same amounts of  
 pigment contamination as the WFK fabric No. 10 C, but no fat components.
Instead of the two soiled fabrics, it is also possible to use the EMPA soiled fabric 101 from the Swiss Federal Material Testing Center in St. Gallen, Switzerland, or WFK soiled fabric 10 D.
The soiled cloths are measured after each wash and replaced by fresh cloths. Redeposition on the three test fabrics is determined after the fifth wash by measuring the reflectance. The whiteness of the unwashed WFK fabric 10 C is 40, that of the unwashed WFK fabric 10 D is 42.5, that of the unwashed pigment-contaminated fabric is 30 and that of the unwashed EMPA fabric 101 is 17.5.
Table 4 shows the various effects of the additives used according to the invention when washing agent formulation IV and various soiled fabrics are employed.
Table 5 shows the effect of additive 3 in the washing agent formulations I-III, V and VI, using the WFK 10 C soiled fabric in combination with the pigment-contaminated fabric.
                                  TABLE 4                                 
__________________________________________________________________________
                       Primary washing                                    
                 Washing                                                  
                       action                                             
       Additive                                                           
            Amount                                                        
                 agent WFK      Redeposition                              
Example                                                                   
       No.  [%]  formulation                                              
                       10 C                                               
                           Pigment                                        
                                PES                                       
                                   PES/C                                  
                                       C                                  
__________________________________________________________________________
Comparison 1                                                              
            1    IV    50  52   48 51  75                                 
Comparison 2                                                              
       HPMC.sup.2                                                         
            0.5  IV    50  51   66 64  79                                 
 1     1    2    IV    67  50   52 61  80                                 
 2     2    2    IV    64  51   50 58  80                                 
 3     3    2    IV    64  50   58 64  80                                 
 4     6    2    IV    57  53   64 66  80                                 
 5     8    2    IV    58  53   60 62  81                                 
 6     11   2    IV    61  53   54 55  80                                 
 7     12   2    IV    53  52   53 60  81                                 
 8     13   2    IV    54  53   54 57  82                                 
 9     14   2    IV    54  54   52 56  82                                 
                       EMPA 101                                           
Comparison 3                                                              
       CMC.sup.1                                                          
            1    IV    42       67 73  81                                 
Comparison 4                                                              
       HPMC.sup.2                                                         
            0.5  IV    39       56 63  78                                 
10     1    2    IV    48       71 75  82                                 
11     2    2    IV    50       69 74  81                                 
12     3    2    IV    46       72 75  82                                 
13     13   2    IV    45       73 75  81                                 
                       WFK 10 D                                           
Comparison 5                                                              
       CMC.sup.1                                                          
            1    IV    71       50 59  82                                 
Comparison 6                                                              
       HPMC.sup.2                                                         
            0.5  IV    69       73 72  83                                 
14     1    2    IV    73       59 64  83                                 
15     3    2    IV    72       62 71  83                                 
16     6    2    IV    71       66 73  83                                 
17     8    2    IV    72       59 68  83                                 
18     11   2    IV    71       55 65  83                                 
19     13   2    IV    72       57 65  83                                 
__________________________________________________________________________
 .sup.1 CMC = Na carboxymethylcellulose                                   
 .sup.2 HPMC = hydroxypropylmethylcellulose                               

              TABLE 5                                                     
______________________________________                                    
                 Primary                                                  
          Washing                                                         
                 washing                                                  
          agent  action                                                   
Com-            formu-   WFK   Pig- Redeposition                          
parison                                                                   
      Example   lation   10C   ment PES  PES/C C                          
______________________________________                                    
7     --    without I      62    40   60   67    79                       
            addi-                                                         
            tive                                                          
--    20    2% of addi-                                                   
                    I      65    43   64   71    80                       
            tive 3                                                        
8     --    with-   II     60    37   57   62    78                       
            out                                                           
            addi-                                                         
            tive                                                          
      21    2% of addi-                                                   
                    II     62    42   60   66    79                       
            tive 3                                                        
9     --    with-   III    60    40   65   62    78                       
            out                                                           
            addi-                                                         
            tive                                                          
--    22    2% of addi-                                                   
                    III    61    41   69   67    79                       
            tive 3                                                        
10    --    with-   V      58    37   36   45    74                       
            out                                                           
            addi-                                                         
            tive                                                          
--    23    2% of addi-                                                   
                    V      62    42   43   55    78                       
            tive 3                                                        
11    --    with-   VI     60    40   40   49    74                       
            out                                                           
            addi-                                                         
            tive                                                          
--    24    2% of addi-                                                   
                    VI     62    42   43   57    78                       
            tive 3                                                        
______________________________________

Claims (8)

We claim:
1. A washing agent based on surfactants, builders, bleaches and conventional additives, which, in order to reinforce the primary washing action and as an antiredeposition agent, contains from 0.5 to 10% by weight, based on the solids, of an amine neutralized or amidated homopolymer of acrylic acid and methacrylic acid, a copolymer of acrylic acid and methacrylic acid, a copolymer which contains, as essential components,
(a) from 10 to 70% by weight of an ethylenically unsaturated dicarboxylic acid of 4 to 6 carbon atoms and
(b) from 90 to 30% by weight of acrylic acid, methacrylic acid, a hydroxy-C2 -C6 -alkyl ester of an ethylenically unsaturated C3 -C5 -carboxylic acid, or mixtures thereof, as copolymerized units,
or mixtures of the homo- and copolymers,
where the homo- and copolymers in the form of free acids have a weight average molecular weight of from 5000 to 500,000, said homo- and copolymers being in the neutralized or amidated form, at least 5% of the carboxyl groups of the homo- and copolymers in each case being neutralized with a primary secondary or tertiary amine of the formula: ##STR5## where R is C8 -C18 -alkyl or R1 --O--CH2 --(CH2)n --, n is from 1 to 3, R1 is C1 -C18 -alkyl, R2 and R3 are each H or C1 -C18 -alkyl, or from 5 to 50% of the said carboxyl groups being in the amidated form derived from a primary or secondary amine of the formula I, or said polymer being both neutralized and amidated.
2. A washing agent as claimed in claim 1, wherein the homopolymer of acrylic acid employed has a weight average molecular weight of from 5000 to 500,000 in the form of the free acid and has been partially or completely neutralized with an amine of the formula I.
3. A washing agent as claimed in claim 1, wherein the copolymer used contains, as essential components,
(a) from 10 to 70% by weight of maleic acid and/or itaconic acid and
(b) from 90 to 30% by weight of acrylic acid, methacrylic acid, hydroxyethyl (meth)acrylate and/or hydroxypropyl (meth)acrylate as copolymerized units,
has a weight average molecular weight of from 10,000 to 200,000 in the form of the free acid and is partially or completely neutralized with an amine of the formula I.
4. A washing agent as claimed in claim 1, wherein the copolymer used contains, as essential components,
(a) from 10 to 70% by weight of maleic acid and
(b) from 90 to 30% by weight of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate and/or hydroxypropyl methacrylate as copolymerized units,
and has a weight average molecular weight of from 10,000 to 200,000 in the form of the free acid, and from 10 to 35% of whose free acid groups have been converted to the corresponding amide with a primary or secondary amine of the formula I.
5. A washing agent as claimed in claim 1, wherein the copolymer used contains, as essential components,
(a) from 10 to 70% by weight of maleic acid and
(b) from 90 to 30% by weight of acrylic acid and/or methacrylic acid as copolymerized units,
and has a weight average molecular weight of from 10,000 to 200,000 in the form of the free acid, and from 10 to 35% of whose free acid groups have been converted to the corresponding amide with a primary or secondary amine of the formula I.
6. A washing agent as claimed in claim 2, wherein an amine of the formula I, where R is C10 -C16 -alkyl and R2 and R3 are each C1 -C4 -alkyl, is employed.
7. A washing agent as claimed in claim 2, wherein an amine of the formula I, where R is C10 -C16 -alkyl and R2 and R3 are each H, is employed.
8. A washing agent as claimed in claim 2, wherein an amine of the formula I, where R is C10 -C16 -alkyl, R2 is H and R3 is C1 -C4 -alkyl, is employed.
US06/888,957 1985-08-08 1986-07-24 Washing agents containing, as additives, carboxyl-containing copolymers which are neutralized or amidated with amines Expired - Fee Related US4702858A (en)

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US4746455A (en) * 1986-06-27 1988-05-24 Kao Corporation Liquid detergent composition for clothing articles
US4814101A (en) * 1987-03-16 1989-03-21 Henkel Kommanditgesellschaft Auf Aktien Zwitterionic polymers and their use in hair treatment preparations
US4897220A (en) * 1987-05-16 1990-01-30 Basf Aktiengesellschaft Detergents containing water-soluble copolymers containing as copolymerized units monomers having two or more ethylenically unsaturated double bonds
US4897215A (en) * 1987-05-16 1990-01-30 Basf Aktiegesellschaft Detergents containing water-soluble copolymers containing as copolymerized units monomers having two or more ethylenically unsaturated double bonds
US5009805A (en) * 1988-11-10 1991-04-23 Basf Aktiengesellschaft Liquid detergent with copolymer additive
US5076957A (en) * 1987-05-06 1991-12-31 Degussa Aktiengesellschaft Phosphate-free detergent builders
US5409629A (en) * 1991-07-19 1995-04-25 Rohm And Haas Company Use of acrylic acid/ethyl acrylate copolymers for enhanced clay soil removal in liquid laundry detergents
US5423999A (en) * 1992-07-01 1995-06-13 Coatex S.A. Stable aqueous suspensions of zeolites, methods of producing same, and use of the suspensions
US5496495A (en) * 1993-08-04 1996-03-05 Chemische Fabrik Stockhausen Gmbh Detergent formulations free of phosphates, zeolites and crystalline layered silicates
US5575946A (en) * 1993-04-28 1996-11-19 Chemische Fabrik Stockhausen Gmbh Water-softening compositions
WO1997011144A1 (en) * 1995-09-20 1997-03-27 Basf Aktiengesellschaft Use of polycarboxylic acid half-amides as additive to washing and cleaning agents
US5739092A (en) * 1992-09-01 1998-04-14 The Procter & Gamble Company Liquid or gel dishwashing detergent containing alkyl ethoxy carboxylate divalent ok ions and alkylpolyethoxypolycarboxylate
US6126757A (en) * 1998-03-16 2000-10-03 Chemtek, Inc. Method of releasing asphalt from equipment using surfactant solutions
US9279097B1 (en) 2014-08-14 2016-03-08 Ecolab USA, Inc. Polymers for industrial laundry detergents

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GB8708312D0 (en) * 1987-04-07 1987-05-13 Unilever Plc Detergent powder composition
GB8918575D0 (en) * 1989-08-15 1989-09-27 Unilever Plc Liquid detergent composition
IE902759A1 (en) * 1990-02-16 1991-08-28 Rohm & Haas Liquid cleaning compositions containing water-soluble¹polymer
US9221967B2 (en) * 2009-12-02 2015-12-29 Huntsman Petrochemical Llc Preparation and use of polymeric dispersant compositions
ES2682176T3 (en) * 2016-01-21 2018-09-19 Henkel Ag & Co. Kgaa Removal of dirt from antiperspirant

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4746455A (en) * 1986-06-27 1988-05-24 Kao Corporation Liquid detergent composition for clothing articles
US4814101A (en) * 1987-03-16 1989-03-21 Henkel Kommanditgesellschaft Auf Aktien Zwitterionic polymers and their use in hair treatment preparations
US5076957A (en) * 1987-05-06 1991-12-31 Degussa Aktiengesellschaft Phosphate-free detergent builders
US4897220A (en) * 1987-05-16 1990-01-30 Basf Aktiengesellschaft Detergents containing water-soluble copolymers containing as copolymerized units monomers having two or more ethylenically unsaturated double bonds
US4897215A (en) * 1987-05-16 1990-01-30 Basf Aktiegesellschaft Detergents containing water-soluble copolymers containing as copolymerized units monomers having two or more ethylenically unsaturated double bonds
US5009805A (en) * 1988-11-10 1991-04-23 Basf Aktiengesellschaft Liquid detergent with copolymer additive
US5409629A (en) * 1991-07-19 1995-04-25 Rohm And Haas Company Use of acrylic acid/ethyl acrylate copolymers for enhanced clay soil removal in liquid laundry detergents
US5423999A (en) * 1992-07-01 1995-06-13 Coatex S.A. Stable aqueous suspensions of zeolites, methods of producing same, and use of the suspensions
US5739092A (en) * 1992-09-01 1998-04-14 The Procter & Gamble Company Liquid or gel dishwashing detergent containing alkyl ethoxy carboxylate divalent ok ions and alkylpolyethoxypolycarboxylate
US5575946A (en) * 1993-04-28 1996-11-19 Chemische Fabrik Stockhausen Gmbh Water-softening compositions
US5496495A (en) * 1993-08-04 1996-03-05 Chemische Fabrik Stockhausen Gmbh Detergent formulations free of phosphates, zeolites and crystalline layered silicates
WO1997011144A1 (en) * 1995-09-20 1997-03-27 Basf Aktiengesellschaft Use of polycarboxylic acid half-amides as additive to washing and cleaning agents
US6126757A (en) * 1998-03-16 2000-10-03 Chemtek, Inc. Method of releasing asphalt from equipment using surfactant solutions
US9279097B1 (en) 2014-08-14 2016-03-08 Ecolab USA, Inc. Polymers for industrial laundry detergents
US9637709B2 (en) 2014-08-14 2017-05-02 Ecolab Usa Inc. Polymers for industrial laundry detergents
US10179889B2 (en) 2014-08-14 2019-01-15 Ecolab Usa Inc. Polymers for industrial laundry detergents

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EP0215251A3 (en) 1987-12-23
EP0215251A2 (en) 1987-03-25
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EP0215251B1 (en) 1989-09-27
ATE46716T1 (en) 1989-10-15

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